JP2663577B2 - Sealing composition - Google Patents
Sealing compositionInfo
- Publication number
- JP2663577B2 JP2663577B2 JP28252188A JP28252188A JP2663577B2 JP 2663577 B2 JP2663577 B2 JP 2663577B2 JP 28252188 A JP28252188 A JP 28252188A JP 28252188 A JP28252188 A JP 28252188A JP 2663577 B2 JP2663577 B2 JP 2663577B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- kovar
- composition
- sealing
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は特にコバール金属の気密封止用ガラス組成物
に関する。The present invention relates to a glass composition for hermetic sealing of Kovar metal in particular.
［従来の技術］ 一般にコバール（Kovar）と呼ばれるFe−Ni−Co合金
は通常Ni27〜28％,Co18〜19％,Fe残部の組成を有し、ガ
ラス封入線材料として用いられる。従来コバールの封着
用には非晶質ガラスおよび結晶化ガラスの両者が知られ
ているが、前者は機械的，熱的強度が低く不充分である
という課題があった。また後者としてはSiO2 9〜21mol
％,B2O3 14〜36％,Al2O3 0〜16％,CaO＋SrO＋BaO＋MgO
9〜56％,ZnO＋CdO 9〜51％からなるガラスがあるが、か
かるガラスは化学的耐久性，コバールとの濡れ性が悪
く、歩留が低いという課題があった。[Prior Art] An Fe-Ni-Co alloy generally called Kovar usually has a composition of 27 to 28% Ni, 18 to 19% Co, and the balance of Fe, and is used as a glass-sealed wire material. Conventionally, both amorphous glass and crystallized glass have been known for sealing Kovar, but the former has a problem that the mechanical and thermal strengths are low and insufficient. As the latter, 9-21 mol of SiO 2
%, B 2 O 3 14~36% , Al 2 O 3 0~16%, CaO + SrO + BaO + MgO
There is a glass composed of 9 to 56% and ZnO + CdO of 9 to 51%. However, such glass has a problem that the chemical durability and the wettability with Kovar are poor and the yield is low.
［発明の解決しようとする問題点］ 本発明は前記結晶化ガラスについて、化学的耐久性特
に耐水性，耐酸性を向上させると共に且つガラスとコバ
ールとの濡れ性の向上をガラス組成面より改善しようと
するものである。[Problems to be Solved by the Invention] The present invention is to improve the chemical durability, especially the water resistance and the acid resistance of the crystallized glass, and to improve the wettability between the glass and Kovar from the aspect of the glass composition. It is assumed that.
［課題を解決するための手段］ 本発明は重量％表示で本質的に SiO2 ８〜15 Al2O3 0.5〜 5 B2O3 20〜27 MgO＋CaO＋SrO＋BaO ３〜10 ZnO 55〜62 SnO2＋TiO2＋ZrO2 0.5〜 3 Ni2O3に換算したニッケルの酸化物＋ Co2O3に換算したコバルトの酸化物＋ Fe2O3に換算した鉄の酸化物 0.01〜 1 からなる結晶性封着用ガラス組成物及び該ガラス組成物
70〜99重量％と残部耐火物フィラーとからなる封着用組
成物を提供するものである。[Means for Solving the Problems] The present invention is essentially SiO 2 8 to 15 Al 2 O 3 0.5 to 5 B 2 O 3 20 to 27 MgO + CaO + SrO + BaO 3 to 10 ZnO 55 to 62 SnO 2 + TiO 2 in weight%. + ZrO 2 0.5 ~ 3 Oxide of nickel converted to Ni 2 O 3 + Oxide of cobalt converted to Co 2 O 3 + Oxide of iron converted to Fe 2 O 3 0.01-1 crystalline sealing glass Composition and glass composition
An object of the present invention is to provide a sealing composition comprising 70 to 99% by weight of a refractory filler.
本発明によるガラスは約750〜950℃の温度で焼成する
ことにより一部が結晶化し気密封着を行うことができ
る。かかる焼成により析出する結晶としてはウィレマイ
トがある。The glass according to the present invention is partially crystallized by firing at a temperature of about 750 to 950 ° C., and can be hermetically sealed. As a crystal precipitated by such firing, there is willemite.
本発明のガラス組成物において、SiO2はガラスのネッ
トワークフォーマーであると共に結晶の主要成分であ
る。８％より少ないとガラス溶解中に失透する恐れがあ
るため好ましくない。一方15％より多いとガラスの軟化
点が高くなり過ぎると共に結晶化を抑制し十分結晶化せ
ず熱膨張係数が45〜55×10-7/℃とならない為好ましく
ない。望ましくは９〜14％の範囲である。In the glass composition of the present invention, SiO 2 is a glass network former and a major component of the crystal. If it is less than 8%, the glass may be devitrified during melting, which is not preferable. On the other hand, if it is more than 15%, the softening point of the glass becomes too high, crystallization is suppressed, crystallization is not sufficiently performed, and the coefficient of thermal expansion does not become 45 to 55 × 10 -7 / ° C. Desirably, it is in the range of 9 to 14%.
Al2O3は結晶化調整剤およびガラスの化学的耐久性向
上剤として含有される。0.5％より少ないと前記効果が
少ない。一方５％より多いとガラスの結晶化が起こりに
くくなり好ましくない。望ましくは１〜４％の範囲であ
る。Al 2 O 3 is contained as a crystallization modifier and a chemical durability enhancer for glass. If the amount is less than 0.5%, the effect is small. On the other hand, if it is more than 5%, crystallization of glass hardly occurs, which is not preferable. Desirably, it is in the range of 1 to 4%.
B2O3はガラスのフラックス剤として用いる。20％より
少ないとガラスの軟化点が高くなり過ぎ好ましくない。
一方27％より多いとガラスの化学的耐久性が著しく低下
する。望ましくは21〜26％の範囲である。B 2 O 3 is used as a fluxing agent for glass. If it is less than 20%, the softening point of the glass is undesirably too high.
On the other hand, if it exceeds 27%, the chemical durability of the glass is significantly reduced. Desirably, it is in the range of 21 to 26%.
MgO＋CaO＋SrO＋BaOはいずれも結晶化調整剤として一
者又は併用で用いる。３％より少ないとその効果は期待
できない。一方10％を越えると熱膨張係数が大きくなり
過ぎ好ましくない。望ましくは４〜８％の範囲である。MgO + CaO + SrO + BaO is used alone or in combination as a crystallization regulator. If it is less than 3%, the effect cannot be expected. On the other hand, if it exceeds 10%, the thermal expansion coefficient becomes too large, which is not preferable. Desirably, it is in the range of 4 to 8%.
ZnOは結晶化物の主結晶であり必須である。その含有
量が55％より少ないと熱膨張係数が大きくなり過ぎ好ま
しくない。62％より多いとガラス溶解中に失透する恐れ
があるため好ましくない。望ましくは57〜60％の範囲で
ある。ZnO is the main crystal of the crystallized product and is essential. If the content is less than 55%, the thermal expansion coefficient becomes too large, which is not preferable. If it is more than 62%, the glass may be devitrified during melting, which is not preferable. Desirably, it is in the range of 57-60%.
SnO2,TiO2,ZrO2はガラスの化学的耐久性を向上させる
目的で含有される。0.5％より少ないとその効果は少な
い。３％より多く含有するとガラスの結晶化が遅くなり
過ぎ十分な結晶化が起こりにくくなるため熱膨張係数が
大きくなり好ましくない。望ましくは１〜２％の範囲で
ある。SnO 2 , TiO 2 , and ZrO 2 are contained for the purpose of improving the chemical durability of glass. If less than 0.5%, the effect is small. If the content is more than 3%, the crystallization of the glass becomes too slow and sufficient crystallization hardly occurs. Desirably, it is in the range of 1 to 2%.
Ni2O3に換算したニッケル酸化物、Co2O3に換算したコ
バルト酸化物、Fe2O3に換算した鉄酸化物はガラスのコ
バール金属への濡れ性向上の目的でその少なくとも一種
含有される。これらの内一者又は併用で0.01％〜１％で
その効果が期待できる。0.01％より少ないと濡れ性を向
上する効果が少なく好ましくない。一方１％より多く含
有すると結晶の析出量が少なくなる熱膨張係数が大きく
なるので好ましくない。望ましくは0.05〜0.5％の範囲
である。この濡れ性はガラスとコバールの接合部の機械
的強度および熱的強度を支配し、従来の知られているガ
ラスにはなく、上記効果が大なる成分である。Nickel oxide converted to Ni 2 O 3 , cobalt oxide converted to Co 2 O 3, and iron oxide converted to Fe 2 O 3 are contained at least one of them for the purpose of improving the wettability of glass to Kovar metal. You. The effect can be expected at 0.01% to 1% by one or a combination of these. If it is less than 0.01%, the effect of improving the wettability is small, which is not preferable. On the other hand, if the content is more than 1%, the amount of precipitated crystals is small, and the coefficient of thermal expansion becomes large. Desirably, it is in the range of 0.05 to 0.5%. This wettability governs the mechanical strength and thermal strength of the joint between glass and Kovar, and is a component that is not found in conventionally known glass but has a large effect.
本発明によるガラス組成物は以上の成分の総量が少な
くとも98％を占め、残部２％未満についてはBi2O3,Ce
O2,MnO2を含有することができる。The glass composition according to the present invention comprises at least 98% of the total amount of the above components, and Bi 2 O 3 , Ce for the remainder of less than 2%.
O 2 and MnO 2 can be contained.
かかるガラス組成物の粉末に対し耐火物フィラーとし
てα−アルミナ，α−石英，ジルコン，コージェライ
ト，安定化ジルコニアから選ばれた少なくとも１種を１
〜30重量％含有することにより、封着部の機械的強度を
向上させることができる。かかる耐火物フィラーの含有
量が１％より少ないと強度向上は期待できない。一方30
％より多いとポーラスとなるため緻密な焼結体から得ら
れず気密不良となるため好ましくない。望ましくは２％
〜25％の範囲である。For the glass composition powder, at least one selected from α-alumina, α-quartz, zircon, cordierite, and stabilized zirconia is used as a refractory filler.
By containing up to 30% by weight, the mechanical strength of the sealing portion can be improved. If the content of the refractory filler is less than 1%, no improvement in strength can be expected. 30
% Is not preferable because it becomes porous and cannot be obtained from a dense sintered body, resulting in poor airtightness. Preferably 2%
It is in the range of ~ 25%.
［作用］ 本発明において、ガラス組成としてSnO2,TiO2あるい
はZrO2成分は前記のとおり化学的耐久性を向上させる目
的で必須であり且つ必然的に長期寿命信頼性に優れる。
また、ニッケル酸化物、コバルト酸化物、鉄酸化物はガ
ラスとコバール金属との界面における反応層の膜厚を制
御すると考えられ、その界面の密着強度に対し最適な反
応層膜厚を生成する。実施例にも述べるようにこれらの
成分が無い従前の結晶化タイプに比し、本発明による組
成物はその引張り強度が向上することが明らかである。
さらに高強度化あるいは焼結体中の泡の成長を抑制する
目的でフィラーを導入することにより、高強度，緻密化
を実現できることを確認した。[Action] In the present invention, SnO 2 , TiO 2 or ZrO 2 component as a glass composition is indispensable for the purpose of improving chemical durability as described above, and inevitably has excellent long-term life reliability.
Nickel oxide, cobalt oxide, and iron oxide are considered to control the thickness of the reaction layer at the interface between glass and Kovar metal, and produce an optimum reaction layer thickness with respect to the adhesion strength at the interface. As described in the examples, it is clear that the composition according to the present invention has an improved tensile strength compared to the conventional crystallization type without these components.
Furthermore, it was confirmed that by introducing a filler for the purpose of increasing the strength or suppressing the growth of bubbles in the sintered body, high strength and densification can be realized.
［実施例］ ガラスの製造に当たっては、所定の組成になるように
各成分原料を秤量・混合し、白金坩堝中にて約1400℃で
２時間撹拌溶解し均質な溶融ガラスを得た。次いでこの
溶融ガラスをフレーク状に形成しボールミル等で平均粒
径２〜12μｍ程度になるように粉砕した。次いでこのガ
ラス粉末と表に示す組成の耐火物フィラー（単位：重量
部）とを混合し、表に示す封着用組成物を得た。フィラ
ーは前記ボールミル粉砕時にガラスフレークと一緒に混
合しても差しつかえない。この封着用組成物について次
の特性を評価したものでその結果も同表へ示した。なお
同表には比較例も併記した。この特性の評価方法は次の
とおりである。[Examples] In the production of glass, each component material was weighed and mixed so as to have a predetermined composition, and stirred and melted in a platinum crucible at about 1400 ° C for 2 hours to obtain a homogeneous molten glass. Next, the molten glass was formed into a flake shape and pulverized by a ball mill or the like so as to have an average particle size of about 2 to 12 μm. Next, this glass powder and a refractory filler (unit: parts by weight) having the composition shown in the table were mixed to obtain a sealing composition shown in the table. The filler may be mixed with the glass flakes during the ball mill pulverization. The following properties of this sealing composition were evaluated, and the results are also shown in the table. The table also shows comparative examples. The evaluation method of this characteristic is as follows.
結晶化温度； 示差分析装置により結晶ピーク点をその温度として表
わした。Crystallization temperature: The crystal peak point was expressed as the temperature by a differential analyzer.
熱膨張係数； 850℃,30分の熱処理した焼結体を加工し、30℃〜400
℃の平均線膨張率を測定した。Coefficient of thermal expansion: 850 ℃, heat treated sintered body for 30 minutes, 30 ℃ ～ 400
The average coefficient of linear expansion at ℃ was measured.
ベンディングによるクラック 厚さ1mmのコバール板に1.4mmφの貫通孔を設け、この
貫通孔に外径0.5mmφ長さ50mmのコバール製ピンを挿通
し、コバール板とピンとを封着用組成物により固定し
た。次いでピンを90度屈曲し封着部におけるクラックの
有無を100倍の実体顕微鏡により観察した。Cracking by bending A 1 mm thick Kovar plate was provided with a 1.4 mmφ through hole, a Kovar pin having an outer diameter of 0.5 mmφ and a length of 50 mm was inserted into the through hole, and the Kovar plate and the pin were fixed with a sealing composition. Next, the pin was bent at 90 degrees, and the presence or absence of cracks in the sealed portion was observed with a 100-fold stereoscopic microscope.
熱衝撃性； −60℃,5分150℃,5分のサイクルを20回実施後の封
着部に入るクラックを観察した。Thermal shock resistance: Cracks were observed in the sealing portion after 20 cycles of −60 ° C., 5 minutes, 150 ° C., 5 minutes.
引張り（破壊）強度（Kg）； 上述のKovarピンを引張りその破壊強度を測定した。Tensile (breaking) strength (Kg): The above Kovar pin was pulled and its breaking strength was measured.
緻密性； 走査型電子顕微鏡により1000倍にして焼結体断面の緻
密性を観察した。Denseness: Denseness of the cross section of the sintered body was observed at a magnification of 1000 with a scanning electron microscope.
気密性； Heリークテスターによりそのリーク量の有無を測定し
た。Airtightness: The presence or absence of the leak amount was measured by a He leak tester.
［発明の効果］ 本発明によれば従前より広く知られていたものに比較
しガラスとコバール界面の密着強度の向上およびフィラ
ー導入による強度の増大および焼結構造の緻密化を実現
し高信頼性を有するコバール気密封止が行える。 [Effects of the Invention] According to the present invention, as compared with those widely known before, the improvement of the adhesion strength at the interface between glass and Kovar, the increase in strength by the introduction of filler and the densification of the sintered structure are realized, and the reliability is high And Kovar hermetic sealing can be performed.
Claims (2)
と残部耐火物フィラーとからなる封着用組成物。2. 70 to 99% by weight of the glass composition according to claim 1.
And a refractory filler as a sealing composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28252188A JP2663577B2 (en) | 1988-11-10 | 1988-11-10 | Sealing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28252188A JP2663577B2 (en) | 1988-11-10 | 1988-11-10 | Sealing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02133336A JPH02133336A (en) | 1990-05-22 |
| JP2663577B2 true JP2663577B2 (en) | 1997-10-15 |
Family
ID=17653535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28252188A Expired - Fee Related JP2663577B2 (en) | 1988-11-10 | 1988-11-10 | Sealing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2663577B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286270A (en) * | 1990-09-07 | 1994-02-15 | Ferro Corporation | Method of forming glass having a Znz SiO4 enamel layer thereon |
| US5208191A (en) * | 1990-09-07 | 1993-05-04 | Ferro Corporation | Crystallizing enamel composition and method of making and using the same |
| US5153150A (en) * | 1990-09-07 | 1992-10-06 | Ferro Corporation | Partially crystallizing enamel containing Zn2 SiO4 to be used for automobile side and rear lights |
| CN100355684C (en) * | 2001-11-30 | 2007-12-19 | 旭硝子株式会社 | Sealing composition and sealing material |
| JPWO2008117797A1 (en) * | 2007-03-27 | 2010-07-15 | 日本山村硝子株式会社 | Lead-free glass composition |
| JP5773128B2 (en) * | 2010-05-10 | 2015-09-02 | 日本電気硝子株式会社 | Method for producing refractory filler |
| US8871664B2 (en) | 2010-05-10 | 2014-10-28 | Nippon Electric Glass Co., Ltd. | Refractory filler, sealing material using same, and manufacturing method for refractory filler |
| WO2011142215A1 (en) * | 2010-05-10 | 2011-11-17 | 日本電気硝子株式会社 | Fire-resistant filler, sealing material using same, and method for producing fire-resistant filler |
| JP5779922B2 (en) * | 2011-03-16 | 2015-09-16 | 日本電気硝子株式会社 | Refractory filler and sealing material using the same |
| JP2012158484A (en) * | 2011-01-31 | 2012-08-23 | Toray Ind Inc | Glass paste, and method for producing plasma display panel using the same |
-
1988
- 1988-11-10 JP JP28252188A patent/JP2663577B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02133336A (en) | 1990-05-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |